Terephthalic acid is commercially produced by oxidation of paraxylene in the presence of a catalyst, such as, for example, Co, Mn, Br and a solvent. Terephthalic acid used in the production of polyester fibers, films, and resins must be further treated to remove impurities present due to the oxidation of paraxylene.
Terephthalic acid (TPA) is an intermediate in the production of polyesters for plastics and fiber applications. Commercial processes for the manufacture of TPA are based on the heavy-metal catalyzed oxidation of p-xylene, generally with a bromide promoter in acetic acid solvent. Due to the limited solubility of TPA in acetic acid under practical oxidation conditions, a slurry of TPA crystals is formed in the oxidation reactor. Typically, the TPA crystals are withdrawn from the reactor and separated from the reaction mother liquor using conventional solid-liquid separation techniques. The mother liquor, which contains most of the catalyst and promoter used in the process, is recycled to the oxidation reactor. Aside from the catalyst and promoter, the mother liquor also contains dissolved TPA and many by-products and impurities. These by-products and impurities arise partially from minor impurities present in the p-xylene feed stream. Other impurities arise due to the incomplete oxidation of p-xylene resulting in partially oxidized products. Still other by-products result from competing side reactions in the oxidation of p-xylene to terephthalic acid.
The solid TPA crystals obtained by solid-liquid separation are generally washed with fresh solvent to displace the major portion of the mother liquor and then dried to remove most of the acetic acid solvent. The dried, crude TPA crystals are contaminated with impurities that were present in the mother liquor since these impurities are co-precipitated with the TPA crystals. Impurities are also present due to occlusion in the TPA crystal structure and due to incomplete removal of the mother liquor by the fresh solvent wash.
Many of the impurities in the mother liquor that are recycled are relatively inert to further oxidation. Such impurities include, for example, isophthalic acid, phthalic acid and trimellitic acid. Impurities, which undergo further oxidation are also present, such as, for example, 4-carboxybenzaldehyde, p-toluic acid and p-tolualdehyde. The concentration of oxidation inert impurities tends to accumulate in the mother liquor. The concentration of these inert impurities will increase in the mother liquor until an equilibrium is reached whereby the amount of each impurity contained in the dry TPA product balances its rate of formation or addition to the oxidation process. The normal level of impurities in crude TPA makes it unsuitable for direct use in most polymer applications.
Traditionally, crude TPA has been purified either by conversion to the corresponding dimethyl ester or by dissolution in water with subsequent hydrogenation over standard hydrogenation catalysts. More recently, secondary oxidative treatments have been used to produce polymer-grade TPA. Irrespective of the method used to purify TPA to render it suitable for use in polyester manufacture, it is desirable to minimize the concentrations of impurities in the mother liquor and thereby facilitate subsequent purification of TPA. In many cases, it is not possible to produce a purified, polymer-grade TPA unless some means for removing impurities from the mother liquor is utilized.
One technique for impurity removal from a recycle stream commonly used in the chemical processing industry is to draw out or “purge” some portion of the recycle stream. Typically, the purge stream is simply disposed of or, if economically justified, subjected to various treatments to remove undesired impurities while recovering valuable components. One example is U.S. Pat. No. 4,939,297 herein incorporated by reference. The amount of purge required for control of impurities is process-dependent; however, a purge amount equal to 10-40% of the total mother liquor is usually sufficient for TPA manufacture. In the production of TPA, the level of mother liquor purge necessary to maintain acceptable impurity concentrations, coupled with the high economic value of the metal catalyst and solvent components of the mother liquor, make simple disposal of the purge stream economically unattractive. Thus, there is a need for a process that recovers essentially all of the expensive metal catalysts and acetic acid contained in the mother liquor while removing a major portion of the impurities present in the purge stream. The metal catalyst should be recovered in an active form suitable for reuse by recycling to the p-xylene oxidation step.
This invention is a marked improvement over a typical purge process. Some of the advantages are:                1) enhanced operability and reliability due to reduction in plugging potential;        2) reduction in overall energy usage.        
The invention enhances the impurity removal efficacy of the process, and the operability of the process compared to the existing processes.